EP0251553A2 - Résine acrylique stabilisée - Google Patents

Résine acrylique stabilisée Download PDF

Info

Publication number
EP0251553A2
EP0251553A2 EP87305324A EP87305324A EP0251553A2 EP 0251553 A2 EP0251553 A2 EP 0251553A2 EP 87305324 A EP87305324 A EP 87305324A EP 87305324 A EP87305324 A EP 87305324A EP 0251553 A2 EP0251553 A2 EP 0251553A2
Authority
EP
European Patent Office
Prior art keywords
acrylic resin
polymer
methacrylate
stabilized
stabilized acrylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87305324A
Other languages
German (de)
English (en)
Other versions
EP0251553A3 (en
EP0251553B1 (fr
EP0251553B2 (fr
Inventor
Harry Joseph Spinelli
Christopher Scopazzi
Joseph Albert Antonelli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25365135&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0251553(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to AT87305324T priority Critical patent/ATE66943T1/de
Publication of EP0251553A2 publication Critical patent/EP0251553A2/fr
Publication of EP0251553A3 publication Critical patent/EP0251553A3/en
Publication of EP0251553B1 publication Critical patent/EP0251553B1/fr
Application granted granted Critical
Publication of EP0251553B2 publication Critical patent/EP0251553B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/923—Treating or preparing a nonaqueous dispersion or emulsion of a solid polymer or specified intermediate condensation product

Definitions

  • Non-aqueous dispersions have previously been found to be useful as rheology control and toughening agents in coating applications.
  • Known non-aqueous dispersions typically comprise a core of material that is not soluble in the solvent system, and, attached to the core, a stabilizing component which is soluble in the solvent system used. In the reactive system, the stabilizer may act as a compatibilizer. The quantity of stabilizer attached to the core is adjusted to solubize the entire structure in the coating composition.
  • non-aqueous dispersions have been prepared using stabilizers having polymerizable functional groups randomly distributed along the chain of the stabilizer. With the random distribution of the polymerizable functional groups along the chain, the effectiveness of the non-aqueous dispersion was less than optimal, and effort has been directed toward the development of non-aqueous dispersions that would provide equivalent or superior performance with a more compact molecule.
  • chain transfer agents for the preparation of stabilizing components used in non-­aqueous dispersions can result in functional groups at the end of the stabilizer molecule, but typically in only 40 to 70 percent of the resulting products. Consequently, substantial quantities of non-polymer­izeable linear polymers are present in the final, stabilized resin prepared from such stabilizers. The presence of such polymers has an undesirable plasti­cizing effect, and would depreciate the resistance of coatings prepared from such resins to solvents such as gasoline.
  • the instant invention provides a stabilized acrylic resin which, through the regularity of the molecular structure, is more effective than similar non-aqueous dispersions previously available.
  • the instant invention provides a stabilized acrylic resin having
  • the instant invention further provides a process for the preparation of a stabilized acrylic resin comprising bringing into contact an unsaturated monomer with a catalyst system in the presence of an initiator containing silicon, tin or germanium and which has a first functional group as part of the structure to give a polymer chain having the first functional group at one end; and bringing the resulting polymer chain into contact, under reaction conditions, with a molecule having a second functional group which is reactive with the first functional group and which can be polymerized with other polymerizable monomers to provide a stabilizing component, and bringing the resulting stabilizing component into contact, under reaction conditions, with unsaturated monomer to produce the stabilized acrylic resin.
  • the present invention is based on the discovery of the beneficial use of a substantially linear stabilizer molecule having a polymerizable functional group at only one end of the molecule.
  • the use of these molecules in the preparation of stabilized acrylic resins results in the attachment of the stabilizing molecules onto the core of insoluble acrylic polymer only at one end, as opposed to both ends or one or more places in the middle of the stabilizing molecule.
  • the stabilizing molecules used in the present invention can be made using Group Transfer Polymerization (GTP), substantially as described in Webster U.S. Patent 4,508,880, hereby incorporated by reference.
  • GTP Group Transfer Polymerization
  • an unsaturated monomer is contacted with an initiator and a catalyst system containing silicon, tin or germanium, under which the polymerization proceeds in a controlled manner, as opposed the random manner typical of polymerization reactions, so that a substantially linear polymer can be prepared having a polymerizable functional group at only one end of the polymer chain and on every polymer chain.
  • a monomer is brought into con­tact with a catalyst and an initiator that has a first functional group as part of its structure. While a wide variety of functional groups can be used, the first functional group is preferably selected from blocked hydroxy, epoxy, blocked acid and aziridine.
  • Monomers which can be used in the present invention include those described in the aforemen­tioned U.S. Patent 4,508,880 at column 8, lines 4 to 22, with the exception of 3-methacryloxypropyl acrylate; and 2-methacryloxyethyl acrylate and linalate.
  • Catalysts which can be used include those disclosed in U.S,. Patent 4,508,880 at column 11, lines 42 to 68, as well as those described in U.S. Patent 4,622,372, hereby incorporated by reference.
  • Initiators which can be used include, for example, 1-(2-trimethyl-siloxyethoxy)-1-trimethyl­siloxy-2-methylpropene and 1-(2-1-ethoxyethoxy]-­ethoxy-1-trimethylsiloxy-2-methypropene. Because of the nature of GTP, the blocked hydroxyl group is left at the beginning of the polymer chain. Thus every chain has one functional group attached to one end. When the polymerization is completed, the blocking group is removed from the end of the polymer chain. This gives a hydroxyl terminated polymer.
  • the functional group is then reacted with compounds that can attach a polymerizable double bond to the polymer.
  • compounds include, for example, any molecule that has a second functional group that can react with the first functional group as well as a group that can be polymerized with other polymerizable monomers.
  • Second functional groups that can be reacted with the first functional groups include epoxy, hydroxy, acid and aziridine, as well as isocyanate, acid chloride, anhydride and ester.
  • Illustrative compounds contain a second functional group, for example, 2-isocyanatoethyl methacrylate, methacryloyl chloride, acryloyl chloride, acrylic acid, methacrylic acid, anhydrides of acrylic and methacrylic acid, maleic anhydride, itaconic anhydride, glycidyl methacrylate, and esters of acrylic and methacrylic acid in transesterification reactions.
  • a second functional group for example, 2-isocyanatoethyl methacrylate, methacryloyl chloride, acryloyl chloride, acrylic acid, methacrylic acid, anhydrides of acrylic and methacrylic acid, maleic anhydride, itaconic anhydride, glycidyl methacrylate, and esters of acrylic and methacrylic acid in transesterification reactions.
  • compounds such as 1,1-bis(trimethylsiloxy)-2-methylpropene can be used as the initiator having the first functional group.
  • the acid terminated poly­mer is reacted with monomers that contain functional groups that can react with acids.
  • monomers includes glycidyl acrylate and methacrylate, aziridinyl acrylate and methacrylate, and the hydroxy esters of acrylic and methacrylic acid.
  • Hydroxy esters which can be used include hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate amd methacrylate, and hydroxybutyl acrylate and methacrylate.
  • initiators that contain a glycidyl or aziridinyl group (e.g., 1-(2,3-epoxypropoxy)-1-­trimethylsiloxy-2-methylpropene and 1-aziridinoxy-1-­trimethylsiloxy-2-methylpropene) can be used to make the initial polymer. These groups can then be reacted with acrylic or methacrylic acid, to put a double bond at one end of the macromonomer.
  • monomers can be polymerized with a blocked diol initiator, e.g., 5-(1-trimethylsiloxy-2-methyl-­1-propenoxy methyl)-2,2-dimethyl-1-,3-dioxolane.
  • a polymer chain After polymerizing the appropriate monomers and deblocking the diol, a polymer chain would be formed that has two hydroxyls attached to one end. These hydroxyls can then be post reacted with compounds previously listed that react with hydroxyls and have a polymerizable group.
  • An example is isocyanatoethyl methacrylate. These will generate a macromonomer with two double bonds at one end. The advantage of having two groups at one end is that there should be a higher probability of incorporating the macromonomer in the second polymerization step.
  • the linear stabilizers so prepared typically have a number average molecular weight of less than 25,000.
  • the size or molecular weight of these polymeric materials can vary, but preferably are substantially uniform in molecular weight.
  • the stabilizing component of the present compositions preferably has a dispersity, measured as the weight average molecular weight divided by the number average molecular weight, of about from 1.0 to 2.5
  • the stabilizing com­ponent prepared as described above, is incorporated into an acrylic polymer.
  • the stabilizer is preferably incorporated into the polymer by polymerizing the polymerizable functional group at the one end of the stabilizer molecule with monomers.
  • Monomers which can be used to prepare the acrylic core include, for example, alkyl methacrylates and acrylates, and examples thereof that can be used to prepare the acrylic polymers are: methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, propyl methacrylate, phenyl methacrylate isobornyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cyclo
  • Adhesion promoting monomers can also be used in the acrylic polymers such as diethyl aminoethyl methacrylate, tertiary butyl aminoethyl methacrylate, 3,(2-methacryloxy ethyl)-2,-spiro cyclohexyl oxazolidene and the like.
  • the acrylic core can be polymerized using conventional, free radical polymerization teechniques or group transfer polymerization techniques as described in the aforementioned Webster patent.
  • the core can also be prepared from monomers having various functional groups such as hydroxy, acid, epoxy, isocyanate, and unsaturated air-drying moieties.
  • Typical hydroxy alkyl acrylates and methacry­lates which can be used to prepare the acrylic polymers are: 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy butyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate, 2-hydroxy butyl methacrylate and the like.
  • acrylic cores which can be incorporated into the acrylic core include glycidyl methacrylate, glycidyl acrylate, isocyanoethyl methacrylate, methacrylic acid, acrylic acid, itaconic acid, itaconic anhydride, and maleic anhydride. These functional monomers can result in acrylic cores that are crosslinked or non-crosslinked.
  • the acrylic polymers can contain about 0.1 to 30% by weight of other constituents such as acrylo­nitrile, methacrylonitrile, acrylamide and methacryl­amide, styrene or substitued styrene such as methyl styrene.
  • Solvents generally used in the polymerization of the acrylic polymer with the stabilizer include any that would give emulsions or dispersions of the stablilized resin.
  • solvents can be used which are solvents for the entire polymer formed so that the final polymer structure is soluble.
  • the resulting stabilized resin formed has a core which is insoluble in the solvents used, having attached thereto the stabilizer which is copolymerized with the core material through the polymerizable functional group at one end of each molecule.
  • the copolymerized stabilizing component is soluble in the solvent and thus acts to stabilize the entire article. Solubility is used in its usual sense, indicating that a molecule of the individual component of the resin would remain as a separate phase in a solvent such as xylene at room temperature if insoluble, and would not form a separate phase if soluble.
  • the stabilized acrylic resins of the present invention provide, in a coating composition using this material as a rheology control agent, better outdoor durability than resins made with styrene or butadiene monomers.
  • the resins exhibit a uniformity which results in reproducible particle size and rheology control.
  • the stabilizers can contain other, non-polymerizable functional groups such as epoxy, amines, blocked hydroxyl acids and amides. Such non-­polymerizable functional groups can further enhance the performance of coatings prepared from these polymers by providing crosslinking sites.
  • the unique physical characteristics of the stabilized acrylic resins of the present invention, and particularly the attachment of a stabilizing resin at only one end of the polymer can be confirmed by differential scanning calorimetry, nuclear magnetic resonance, gas chromatography and infrared analysis.
  • the stabilized resins of the present invention are substantially free from non-polymerizable linear polymer, that is, linear stabilizer having no double bond in its structure that is capable of further polymerization. This is a function of the linear stabilizer components each having a functional group at one end of the stabilizer molecule. Accordingly, the concentration of non-polymerizable linear polymer is typically substantially less than 1 percent.
  • the stabilized acrylic resins of the present invention exhibit a substantially lower concentration of ungrafted material than stabilized acrylic resins prepared, for example, using chain transfer techniques.
  • the stabilizing resin often contains a polymerizable double bond, but the double bond is not attached to the end of the chain, which accordingly results in at least about 20 percent of ungrafted material in the final stabilized resin.
  • the percentage of ungrafted polymer in the present invention is typically less than about 10 percent and often less than about 5 percent by weight. The substantial absence of non-polymeriza­ble linear polymer is believed to be a function of the method of preparation of the present resins.
  • the stabilized acrylic resins of the present invention can be used as rheology control and toughen­ing agents in conventional coating applications.
  • the resins will be present in a concentra­tion of about from 1 to 80 percent by weight, and preferably about from 10 to 40 percent by weight, of the total coating compostion.
  • the resins can be used effectively in a wide variety of coating compositions, including unicoats, basecoats and clear coatings. When used in clear coatings, the resins provide exceptionally good rheology control.
  • the resins can also be used in molding resins and acrylate sheeting, providing rheoloy control in the course of preparation of such shaped articles and enhanced toughness in the finished product.
  • a macromonomer was prepared that has a P-NBMA composition and a methacrylate double bond at one end.
  • the macromonomer is made using a blocked hydroxyl initiator, followed by polymerization of NBMA, removal of the blocking group, and finally reacting the hydroxyl with disocyanatoethyl methacrylate.
  • the polymer solution was heated at 60 degrees C for 2 hours.
  • An IR spectrum then showed no OH band at 3550 cm (-1) but a smaller NCO ban at 2265 cm (-1), confirming that all hydroxyls on the polymer had been reacted with the IEM, thus placing one polymerizable group on every polymer chain.
  • Methanol, 50 ml was then added to the polymer solution and the solution was heated to 60 degrees C for 2 hours.
  • AN IR spectrum showed no NCO band at 2265 cm (-1), a small OH band (from the methanol) at 3550 cm (-1), and a carbon-carbon double bond (from the methacrylate functionality at 1640 cm (-1) confirming that any excess IEM has been quenched.
  • a non-aqueous dispersion was prepared using the NBMA macromonomer as the stabilizing resin.
  • the NAD was prepared by copolymerizing the NBMA macromonomer with other monomers in a free radical process.
  • a 1 liter flask equipped with heating mantle, reflux condenser, and addition funnels was charged with 125.02 gm of NBMA macromonomer solution prepared above, 91.32 gm of xylene, 12.32 gm of i-propanol, 221.08 gm of heptane, and 17.56 gm of aliphatic hydrocarbon (bp 155-190).
  • the flask was heated to reflux and 0.32 gm of t-butyl peroctoate was added. Feed I was then begun.
  • Feed I consisted of 8.63 gm of 30 methacrylic acid, 53.94 gm of hydroxyethyl acrylate, 100.32 gm of methyl methacrylate, 38.84 gm of methyl acrylate, 10.79 gm of stryene, 3.29 gm of glycidyl methacrylate, 62.77 gm of NBMA macromonomer solution prepared above, 8.16 gm of xylene, 43.84 gnm of 35 aliphatic hydrocarbon (bp 155-190), 8.75 gm of i-butanol, and 3.24 gm of t-butyl peroctoate. Feed I was added over 3.5 hours.
  • Feed II was begun following a 45 minute hold period after Feed I was completed. Feed II was added over an additional 1.5 hours. Feed II consisted of 11.57 gm of i-butanol and 2.12 gm of t-butyl peroctoate. The flask was held at reflux for 1 hour following the completion of Feed II. The resulting polymer had a composition of NBMA/MMA/MA/HEA/STY/GMA/MAA 35.1/30.2/11.7/16.2/3.2/1.0/2.6.
  • a coating composition was made from a NAD prepared as described above that is stabilized by a NBMA macromonomer.
  • the NAD provided rheology control and prevented the coating from sagging once it was applied. In addition, flake disorientation in the coating composition was reduced.
  • a silver metallic coating was made by blend­ing:
  • This coating was 45.1% solidds and had a pigment-to-binder ratio (P/B) of 15/100 with aluminum flake as the only pigment. It contained 20 parts of NAD rheology control agent prepared using the NBMA macromonomer.
  • the coating was applied as a basecoat at a thickness of 0.8 mils on primed steel and aluminum panels. The basecoat was covered with a clear coat that consisted of a standard acrylic resin, melamine crosslinker, and rheology control agents. Panels were baked for 30 minutes at 250 degrees F. The films were hard, gloss coatings that could be used in applications such as automotive or appliance finishes. Basecoats that did not use the NAD made from the NBMA macro­monomer had poor appearances.
  • a macromonomer was prepared that had a P-EHMA composition and a methacrylate double bond at one end.
  • the macromonomer was made using a blocked hydroxyl initiator, polymerization of EHMA, removal of the blocking group, and finally reacting the hydroxyl with isocyanatoethyl methacrylate.
  • Feed II 4.5 ml of 1.0 M tetrabutylammonium m-chloro-­benzoate and 14.9 gm of glyme, was begun simultaneously with Feed I.
  • Feed II was added over 60 minutes.
  • 20 gm of methanol was added to quench the reaction.
  • To the polymer solution was added 34.0 gm of water and 102.17 gm of isopropanol. The polymer solution was then refluxed for 5 hours.
  • a macromonomer was prepared that had a NBMA composition with a methacrylate double bond at one end of the chain and an epoxy group at the end.
  • a 1 liter flask was charged with 121.1 gm of toluene, 10.91 gm of 1-(2-trimethylsiloxyethoxy)-­1-trimethylsiloxy-2-methyl propene, 0.040 m, and 0.44 ml of a 1.0 M solution of tetrabutylammonium m-chlorobenzoate dissolved in acetonitrile. Feed I, 178.5 gm of n-butyl methacrylate, was added over 31 minutes.
  • the macromonomer can be reacted with acrylic resin as described in Example 1 to form a stabilized acrylic resin. If this stabilized acrylic resin is used in the preparation of a coating composition as described in Example 1, similar results will be obtained.
  • a NBMA macromonomer was prepared using a blocked acid initiator.
  • the polymer was made by starting with a blocked acid initiator, polymerizing NBMA, deblocking the acid group, and reacting the acid terminated polymer with glycidyl methacrylate. This gave a NBMA macromonomer that has a methacrylate double bond at one end.
  • Example 2 Using a procedure similar to that given in Example 2, a 1 liter flask was charged with 170.2 gm of toluene, 30.1 gm of propylene carbonate, 1.22 gm of xylene 17.41 gm of 1-(bis-trimethyl­siloxy)-2-methyl propene and 1.2 ml of a 1.0 M solution of tetrabutylammonium m-chlorobenzoate dissolved in acetonitrile. Feed I, 294.9 gm of n-butyl methacrylate, was added ovver 60 minutes.
  • Feed II 1 ml of 1.0 M tetrabutylammonium m-chloro­benzoate and 4.46 gm of toluene, would begin simultaneously with Feed I.
  • Feed II wa added over 90 minutes.
  • 6 gm of water and 180 gm of isopropanol was added to quench the reaction.
  • the polymer solution was refluxed for 1 hour. This gave a P-NBMA polymer that has one acid group at an end of the chain (Acid No. 7.25).
  • Glycidyl methacrylate, 27.8 gm, and 0.36 gm of di-t-butyl catechol was added to the polymer solution.
  • the solution was then heated for 4 hours.
  • the Acid No. was reduced to less than 1.0, confirming that all acid groups had reacted with the epoxy, placing one poly­merizable group at the end of every polymer chain.
  • the final product is a 3500 Mn P-NBMA macromonomer that has one methacrylate double bond at the end of the chain.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Dental Preparations (AREA)
  • Materials For Medical Uses (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Road Signs Or Road Markings (AREA)
  • Polymerization Catalysts (AREA)
EP87305324A 1986-06-17 1987-06-16 Résine acrylique stabilisée Expired - Lifetime EP0251553B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87305324T ATE66943T1 (de) 1986-06-17 1987-06-16 Stabilisiertes acrylharz.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/875,059 US4746714A (en) 1986-06-17 1986-06-17 Stabilized acrylic resin
US875059 1986-06-17

Publications (4)

Publication Number Publication Date
EP0251553A2 true EP0251553A2 (fr) 1988-01-07
EP0251553A3 EP0251553A3 (en) 1989-12-13
EP0251553B1 EP0251553B1 (fr) 1991-09-04
EP0251553B2 EP0251553B2 (fr) 1995-02-08

Family

ID=25365135

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87305324A Expired - Lifetime EP0251553B2 (fr) 1986-06-17 1987-06-16 Résine acrylique stabilisée

Country Status (16)

Country Link
US (1) US4746714A (fr)
EP (1) EP0251553B2 (fr)
JP (1) JP2532472B2 (fr)
KR (1) KR940010340B1 (fr)
AT (1) ATE66943T1 (fr)
AU (1) AU597534B2 (fr)
BR (1) BR8703029A (fr)
CA (1) CA1276332C (fr)
DE (1) DE3772652D1 (fr)
DK (1) DK305487A (fr)
ES (1) ES2025163T5 (fr)
HK (1) HK100391A (fr)
MX (1) MX165861B (fr)
NO (1) NO168112C (fr)
SG (1) SG94091G (fr)
ZA (1) ZA874323B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0523267A1 (fr) * 1990-05-10 1993-01-20 E.I. Du Pont De Nemours And Company Composition de revêtement à base d'un polymère acrylique, d'un agent réticulant et d'un oligomère silane
WO1993013111A1 (fr) * 1991-12-24 1993-07-08 E.I. Du Pont De Nemours And Company Doubles microparticlues stabilisees
WO1994021701A1 (fr) * 1991-12-24 1994-09-29 E.I. Du Pont De Nemours And Company Dispersions de pigments aqueuses comportant un copolymere greffe
WO1996001880A1 (fr) * 1994-07-08 1996-01-25 E.I. Du Pont De Nemours And Company Compositions de revetements durables
US5711940A (en) * 1993-10-01 1998-01-27 Lvmh Recherche Stable microdispersions and microgels based on acrylic polymers, method for obtaining them and compositions, particularly cosmetic compositions, containing them
WO1998027173A1 (fr) * 1996-12-17 1998-06-25 E.I. Du Pont De Nemours And Company Compositions de revetement contenant des polymeres disperses non aqueux a temperature de transition vitreuse elevee
DE19908627A1 (de) * 1999-02-27 2000-08-31 Herberts Gmbh & Co Kg Überzugsmittel und deren Verwendung bei der Mehrschichtlackierung

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2648853B2 (ja) * 1987-04-22 1997-09-03 日本ペイント株式会社 複合三次元化樹脂粒子ならびにその製法
US5010140A (en) * 1989-05-31 1991-04-23 E. I. Du Pont De Nemours And Company Process for preparing stabilized polymer dispersion
DE69133360T2 (de) * 1991-02-15 2004-12-09 E.I. Du Pont De Nemours And Co., Wilmington Stabilisierte Polymerdispersion
US5780553A (en) * 1993-07-30 1998-07-14 University Of North Carolina At Chapel Hill Heterogeneous polymerizations in carbon dioxide
TW287192B (fr) * 1994-01-21 1996-10-01 Ei Du Pont De Nemours Amd Co
US5985956A (en) * 1996-02-14 1999-11-16 E. I. Du Pont De Nemours And Company Crack-resistant one-package coating composition
US5639841A (en) * 1995-02-28 1997-06-17 Union Carbide Chemicals & Plastics Technology Corporation Polymers containing macromonomer mixtures
JPH09241480A (ja) * 1996-03-04 1997-09-16 Nof Corp 熱硬化性組成物、それを用いた塗料組成物、並びにその塗装方法と塗装物品
US5770646A (en) * 1996-10-29 1998-06-23 E. I. Du Pont De Nemours And Company Aqueous branched polymer dispersant for hydrophobic materials
JP4421614B2 (ja) * 2004-08-13 2010-02-24 日本曹達株式会社 スターポリマー、酸分解性樹脂組成物、レジスト組成物およびジ（メタ）アクリレート化合物
KR100802060B1 (ko) 2007-02-02 2008-02-11 삼성전자주식회사 과도한 특정 스트레스 항목의 인가를 방지하는 반도체메모리 장치 및 그것의 테스트 방법
US9434828B2 (en) 2010-12-08 2016-09-06 Ppg Industries Ohio, Inc. Non-aqueous dispersions comprising a nonlinear acrylic stabilizer
US9346959B2 (en) 2010-12-08 2016-05-24 Ppg Industries Ohio, Inc. Non-aqueous dispersions comprising a nonlinear acrylic stabilizer
EP3478751A4 (fr) 2016-07-02 2019-07-17 Rheomod De Mexico, S.A.P.I. De C.V. Polymères greffés

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1416397A (fr) * 1963-08-06 1965-11-05 Ici Ltd Préparation de polymères d'addition comportant un groupe carboxyle terminal
LU68147A1 (fr) * 1972-08-04 1973-10-16
US3928255A (en) * 1971-02-22 1975-12-23 Cpc International Inc Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation
GB1419669A (en) * 1972-12-29 1975-12-31 Kuraray Co Metetials for self-reinforcing hydrogels

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508880A (en) * 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4528317A (en) * 1983-01-05 1985-07-09 Ford Motor Company Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers II
US4533695A (en) * 1983-01-05 1985-08-06 Ford Motor Company Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers II
US4605720A (en) * 1983-02-23 1986-08-12 Ford Motor Company Preparation of nonaqueous dispersions with the use of monofunctional stabilizer
US4493914A (en) * 1983-02-23 1985-01-15 Ford Motor Company Stabilized dispersion of cross-linked polymer particles
US4530959A (en) * 1984-03-08 1985-07-23 The Goodyear Tire & Rubber Company Pneumatic tire with tread of medium vinyl polybutadiene/rubber blend

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1416397A (fr) * 1963-08-06 1965-11-05 Ici Ltd Préparation de polymères d'addition comportant un groupe carboxyle terminal
US3928255A (en) * 1971-02-22 1975-12-23 Cpc International Inc Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation
LU68147A1 (fr) * 1972-08-04 1973-10-16
GB1419669A (en) * 1972-12-29 1975-12-31 Kuraray Co Metetials for self-reinforcing hydrogels

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MACROMOLECULES, vol. 13, 1980, pages 216-221, American Chemical Society; K. ITO et al.: "Syntheses of methyl methacrylate-stearyl methacrylate graft copolymers and characterization by inverse gas chromatography" *
MAKROMOLEKULARE CHEMIE, vol. 186, no. 2, February 1985, pages 261-271, Basel, CH; C. BONARDI et al.: "Synthèse et copolymérisation avec l'acrylamide de macromonomères d'acrylate de dodécyle" *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0523267A1 (fr) * 1990-05-10 1993-01-20 E.I. Du Pont De Nemours And Company Composition de revêtement à base d'un polymère acrylique, d'un agent réticulant et d'un oligomère silane
WO1993013111A1 (fr) * 1991-12-24 1993-07-08 E.I. Du Pont De Nemours And Company Doubles microparticlues stabilisees
WO1994021701A1 (fr) * 1991-12-24 1994-09-29 E.I. Du Pont De Nemours And Company Dispersions de pigments aqueuses comportant un copolymere greffe
US5711940A (en) * 1993-10-01 1998-01-27 Lvmh Recherche Stable microdispersions and microgels based on acrylic polymers, method for obtaining them and compositions, particularly cosmetic compositions, containing them
WO1996001880A1 (fr) * 1994-07-08 1996-01-25 E.I. Du Pont De Nemours And Company Compositions de revetements durables
CN1061072C (zh) * 1994-07-08 2001-01-24 纳幕尔杜邦公司 耐久涂料组合物
WO1998027173A1 (fr) * 1996-12-17 1998-06-25 E.I. Du Pont De Nemours And Company Compositions de revetement contenant des polymeres disperses non aqueux a temperature de transition vitreuse elevee
DE19908627A1 (de) * 1999-02-27 2000-08-31 Herberts Gmbh & Co Kg Überzugsmittel und deren Verwendung bei der Mehrschichtlackierung
DE19908627C2 (de) * 1999-02-27 2001-06-07 Herberts Gmbh & Co Kg Überzugsmittel und deren Verwendung bei der Mehrschichtlackierung

Also Published As

Publication number Publication date
JP2532472B2 (ja) 1996-09-11
AU7442087A (en) 1987-12-24
KR940010340B1 (ko) 1994-10-22
AU597534B2 (en) 1990-05-31
JPS62297306A (ja) 1987-12-24
KR880000485A (ko) 1988-03-26
MX165861B (es) 1992-12-08
NO168112B (no) 1991-10-07
EP0251553A3 (en) 1989-12-13
EP0251553B1 (fr) 1991-09-04
ES2025163B3 (es) 1992-03-16
DK305487A (da) 1987-12-18
DE3772652D1 (de) 1991-10-10
NO872514L (no) 1987-12-18
SG94091G (en) 1991-12-13
HK100391A (en) 1991-12-20
EP0251553B2 (fr) 1995-02-08
BR8703029A (pt) 1988-03-08
CA1276332C (fr) 1990-11-13
ATE66943T1 (de) 1991-09-15
ES2025163T5 (es) 1995-08-16
NO872514D0 (no) 1987-06-16
DK305487D0 (da) 1987-06-16
ZA874323B (en) 1989-02-22
NO168112C (no) 1992-01-15
US4746714A (en) 1988-05-24

Similar Documents

Publication Publication Date Title
EP0251553B1 (fr) Résine acrylique stabilisée
US5534598A (en) Hydroxy-functional acrylate resins
US5310807A (en) Star polymers made from macromonomers made by cobalt chain transfer process
EP0679664B1 (fr) Polymères d'allyl alcool propoxylé
US5391631A (en) Vinyl polymers produced by a two-stage procedure and their use as surface coating binders
EP0770101B1 (fr) Compositions catalytiques et revetements realises a partir de ces compositions
US4415681A (en) Stabilized crosslinked dispersion
US4611028A (en) Polymeric dispersion stabilizer and stable dispersions prepared therefrom
EP0703250B1 (fr) Polymères d'esters allyliques et d'alcool allylique ou d'alcool allylique propoxylé
US5310813A (en) Thermosetting coating resin and process for producing the same
EP0465835A1 (fr) Polymères vivantes anioniques, leurs dérivés et compositions les contenant
US5480954A (en) Allyl ester copolymers with allylic alcohols or propoxylated allylic alcohols
JP2796883B2 (ja) 溶液型塗料
EP0628579B1 (fr) Résine liquide, procédé de sa préparation et son usage
JPS59213701A (ja) 反応性アクリル重合体組成物
US5239032A (en) Heterofunctional macromer compound, its preparation and polymer derived therefrom
US5239031A (en) Heterofunctional macromer compound, its preparation and polymer derived therefrom
US20090318648A1 (en) Media-resistant coating resins

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19900521

17Q First examination report despatched

Effective date: 19900913

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 66943

Country of ref document: AT

Date of ref document: 19910915

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3772652

Country of ref document: DE

Date of ref document: 19911010

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920630

Ref country code: LI

Effective date: 19920630

Ref country code: CH

Effective date: 19920630

26 Opposition filed

Opponent name: ROEHM GMBH

Effective date: 19920603

NLR1 Nl: opposition has been filed with the epo

Opponent name: ROEHM GMBH

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19940412

Year of fee payment: 8

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

EAL Se: european patent in force in sweden

Ref document number: 87305324.3

27A Patent maintained in amended form

Effective date: 19950208

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

ITF It: translation for a ep patent filed
NLR2 Nl: decision of opposition
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19950508

ET3 Fr: translation filed ** decision concerning opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 19950816

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20050728

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060604

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20060607

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060608

Year of fee payment: 20

Ref country code: DE

Payment date: 20060608

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060614

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060630

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20060816

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20070616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20070618

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 20070616

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20070615

BE20 Be: patent expired

Owner name: E.I. *DU PONT DE NEMOURS AND CY

Effective date: 20070616